psyloxy (Hive Addict) 09-09-03 21:55 No 458067 |
novel synthesis of O-Acetyl-Mandelonitrile (Rated as: good idea!) |
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Synthesis of 3,4,5-trimethoxybenzaldehyde cyanohydrin acetate and subsequent reduction thereof with Pd/H2 @ 1atm is described in ../rhodium /mescaly Yield of acetylated mandelonitrile is only ~66% from the benzaldehyde. It involves the use of KCN. In Ref[1] O-acetyl-mandelonitrile is prepared in 90% yield at ambient temp in 1 hour from benzaldehyde, 2-oxo-propionitrile and aq. K2CO3 soln. in acetonitrile. No, I have not read the article. Yes, I want to know what it says,too. Now, what is 2-oxo-propionitrile and how is it made ? I hope you can guess it's structure from the following little ascii drawing: H3C-C=O
[1] Okimoto, Mitsuhiro; Chiba, Toshiro; SYNTBF; Synthesis; EN; 10; 1996; 1188-1190. [2] Smidt; Sieber; ANCEAD; Angew.Chem.; 71; 1959; 626. [3] Mukherjee, Jogeshwar; Rogers, Janice I.; Khalifah, Raja G.; Everett, Grover W.; JACSAT; J.Amer.Chem.Soc.; EN; 109; 23; 1987; 7232-7233 [4] Scholl; MOCMB7; Monatsh.Chem.; 39; 1918; 238. [5] Claisen; Manasse; CHBEAM; Chem.Ber.; 20; 1887; 2196 [6] Tajbakhsh, M.; Bakooie, H.; Ghassemzadeh, M.; Beheshtiha, Y. Sh.; Heravi, M. M.; IJSBDB; Indian J.Chem.Sect.B; EN; 40; 12; 2001; 1232 - 1233 [7] Slater; JCSOA9; J.Chem.Soc.; 117; 1920; 589. [8] Kuester; HSZPAZ; Hoppe-Seyler's Z.Physiol.Chem.; 155; 1926; 180. [9] Schmidt; ARPMAS; Arch.Pharm.(Weinheim Ger.); 250; 1912 --psyloxy-- |
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Rhodium (Chief Bee) 09-09-03 23:30 No 458084 |
PhCHO + AcCN -> O-Acetyl-Mandelonitrile (Rated as: good read) |
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A Convenient and Improved Method for the Preparation of Cyanohydrin Esters from Acyl Cyanides and Aldehydes M. Okimoto & T. Chiba Synthesis (10), 1188-1190 (1996) (../rhodium/pdf /mandelonitri |
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psyloxy (Hive Addict) 09-10-03 03:14 No 458142 |
refs for the preparation of benzoylcyanide | |||||||
So the autors indicate Ph-CO-CN can also be used. That made psyloxy look into preparation methods for this compound. Here's what he found. [1]First let's prepare some acetoneoxime from, you guessed it, acetone and NH2OH.HCl. With the aid of Na2CO3 and hot aqu. EtOH 96% yield can be had in 24h. In the 2nd step acetophenone is first oxidised to phenylglyoxaldehyde by DMSO/HBr then hydrated with H2O to phenylglyoxylhydrate, refer to ex. XI in Patent US3434064 [2]Said phenylglyoxalhydrate is then reacted with the aforementioned acetoneoxime + HCl for 2h in 50°C H2O to give a 91% yield of oxo-phenyl-acetaldehyde oxime [3] Finally oxo-phenyl-acetaldehyde oxime is dehydrated with Ac2O to form oxo-phenylacetonitril Now that reads 4 rxns at first sight. But look at them. Simple chems, simple (+mild) rxns, simple workup... pure chemical simplicity, no need to fool around with KCN, not even alkylnitrites! Well, from my theoretical point of view it all looks fine and dandy [1]Langhals, Heinz; Range, Guenter; Wistuba, Eckehardt; Ruechardt, Christoph; CHBEAM; Chem.Ber.; GE; 114; 12; 1981; 3813-3830. [2]Meester, Johan W. G. De; Plas, Henk C. van der; Middelhoven, Wouter J.; JHTCAD; J.Heterocycl.Chem.; EN; 24; 1987; 441-451. [3]Hegarty, Anthony F.; Tuohey, Patrick J.; JCPKBH; J.Chem.Soc.Perkin Trans.2; EN; 1980; 1313-1317 --psyloxy-- |
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